On the definition of the excess permittivity of a fluid mixture. II

In a previous work, an ideal fluid mixture is assumed to be a homogeneous linear and isotropic system that verifies the following conditions: (I) no interaction between molecules, (II) point-like molecules and (III) under fixed temperature and pressure conditions the number of molecules per unit volume is the same for both the individual components and the mixture. It was shown that for such ideal mixture the permittivity is the sum of the individual permittivities weighted with the mole fractions of the components.In this work it is shown that independently of the latter assumption the permittivity of the system can be expressed as the sum of the individual permittivities weighted with the volume fractions of the components.     

Studies on the conformational isomers of 2-anilinopyridines and related compounds

Infrared spectra in the N---H stretching region of several nitro-substituted 2-anilinopyridines and related compounds were measured under the conditions in which no intermolecular interaction is probable, and the reasons for the splitting of the N---H bands have been discussed. From the solvent and temperature dependence of the N---H stretching spectra, it is concluded that the splitting is due to the existence of rotational isomers. The assignments of these absorptions are given and some evidence to support the above conclusions is presented.     

Multipole interaction in high energy approximation. Calculation of the total collision cross section

For molecules of cylindrical symmetry the total collision cross section is calculated in the high energy approximation, taking into account various long range intermolecular interactions. Results are obtained for the limiting cases that the rotational motion of the molecules is fast or slow with respect to the duration of the molecular interaction. The assumption is made that either one multipole term of the intermolecular potential predominates or that all multipole terms can essentially be treated as a small perturbation of the van der Waals r^?6 interaction.     

A model for the creep of oriented high-modulus fibers

Recently it has been shown that the creep of oriented high-modulus fibers satisfies a logarithmic time law over very long time intervals. Moreover, the modulus of these fibers increases due to the creep. This was interpreted by the annihilation of conformation defects during creep. In structures with strong intermolecular interactions as in aramides, however, the direct annihilation of defects is difficult to explain. Moreover a direct annihilation leads to a false time law if no further assumption about the properties of the defects are made. In this paper a model for the transport of conformation defects in oriented polymer chains imbedded into an oriented fibrillary structure with strong intermolecular interactions is presented. This modified transport model leads directly to the experimentally observed time law without any further assumptions about the defect properties.     

Tracing the critical loci of binary fluid mixtures using molecular simulation

Monte Carlo simulations are used to trace the critical loci for a number of binary mixtures. In particular, we use grand canonical Monte Carlo (GCMC) simulations with histogram reweighting and mixed-field finite-size scaling to determine the mixture critical lines. Two different classes of criticality are investigated. A mixture of methane and ethane displays type I criticality, exhibiting continuous mixing between the two species across the entire composition range. A methane-water mixture shows type IIIb criticality, with a discontinuity in the critical locus. Quantitative agreement is found between simulation and experimental critical loci for the methane-ethane system using no adjustable parameters for interactions in the mixture. For the water-methane system, we investigate the effect of the combining rules for the intermolecular interaction between the two species on the mixture critical locus. We also investigate several potentials for methane: a nonpolar exponential-6, an octopolar fixed partial charge, and a polarizable fluctuating charge model. Qualitative agreement between simulations and experiments is found for all potentials, but none are able to quantitatively capture the abrupt increase in the critical temperature as methane is added to the system.     

Self-Diffusion Coefficients for Pure and Mixed Adsorbate Fluids in Narrow Pores

The equilibrium distribution and the concentration dependence of the local and average self-diffusion coefficients for pure fluid and binary mixture components in narrow slitlike pores were analyzed. The coefficients were calculated using the lattice gas model in the quasi-chemical approximation on the assumption of a spherical shape and approximately equal sizes of the components. For the pure adsorbate, these calculations were compared with molecular dynamics simulations. Both methods gave similar concentration profile changes and dynamic characteristics of interlayer particle redistributions in strong nonuniform adsorption fields for dense fluids. A satisfactory agreement was obtained for the temperature dependences of the self-diffusion coefficients along the pore axis. The influence of the molecule–wall potential and of intermolecular interaction were considered. The self-diffusion coefficients of the adsorbate were shown to strongly depend on the density of the mixture and the distance from pore walls.     

Thermal and volumetric properties of methanol–hexamethylphosphortriamide mixtures under standard conditions

Enthalpic and volumetric characteristics of mixing in a methanol (MeOH)–hexamethylphosphortriamide (HMPT, 2) mixture are studied. Based on an analysis of concentration changes in the obtained data and the calculated partial molar characteristics, it is shown that at 0.2 molar fractions > х ₂ > 0.7 molar fractions, the variation in the composition of the mixture slightly alters the character of intermolecular interactions characteristic of pure components. It is found that MeOH–HMPT mixtures experience most changes in intermolecular interaction and structure within the range of 0.2–0.7 molar fractions of HMPT.

     

Hard and Soft - Core Equations of State for Simple Fluids: VI. General Theory of Termination Temperatures,and a Validity Criterion for the Second Virial Coefficient

Abstract

A general proof is given that the classical second virial coefficient satisfies the requirement for the non-existence of a termination point of any locus of C_v extrema. This validity criterion is applied to some proposed forms for the second virial coefficient. The order of the termination temperatures is verified for a fairly general intermolecular potential. In particular a proof is given that T_F lies between T_C and T_A. Also the hard-core limit of the ratio T_D/T_A(～2) is examined briefly.     

On the number of spin functions in the first order interaction space

A proof is given that in a configuration interaction method the first-order interaction space contains at most only twice as many spin functions as the zeroth-order space. This allows for a dramatic reduction of the size of CI expansion. For most of the high-spin systems only two spin functions for each configuration are needed.     

Influence of intermolecular interaction with the eluent on the retention and selectivity in liquid chromatography

Summary The influence of substance — eluent (water-isopropanol mixture) intermolecular interaction on the retention and selectivity of separation in liquid chromatography on silica gel with silanized surface has been investigated for benzene and toluene derivatives. The interaction greatly depends on the nature of the polar functional groups, their position in the benzene ring and the existence of intramolecular interaction.     

On the original proof by reductio ad absurdum of the Hohenberg–Kohn theorem for many‐electron Coulomb systems

It is shown that, for isolated many‐electron Coulomb systems with Coulombic external potentials, the usual reductio ad absurdum proof of the Hohenberg–Kohn theorem is unsatisfactory since the to‐be‐refuted assumption made about the one‐electron densities and the assumption about the external potentials are not compatible with the Kato cusp condition. The theorem is, however, provable by more sophisticated means, and it is shown here that the Kato cusp condition actually leads to a satisfactory proof. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Theory Studies on the Intermolecular Interactions of Urea Nitrate with RDX

Six fully optimized geometries of urea nitrate cation and RDX complexes have been obtained with DFT-B3LYP and MP2 methods at the 6-311++G** level. The intermolecular interaction energies have been calculated with basis set superposition error (BSSE) and zero point energy (ZPE) correction. The nature of intermolecular interaction has been revealed by the analysis of AIM and NBO. The results indicate that the greatest binding energy of urea nitrate with RDX is –82.47kJ/mol. The O–H…O and N–H…O hydrogen bonds are important intermolecular interactions of urea nitrate cation with RDX, and the origin of hydrogen bonds is the oxygen atom offering its lone-pair electrons to the σ(O-H)* or σ(O-H)* antibonding orbital. The intermolecular interactions strengthen the N–NO2 bond, leading to the reduced sensitivity of urea nitrate and RDX mixture explosive.     

聚乙烯醇与葡激酶的相互作用及其对葡激酶二级结构的影响

在生理条件下, 使用凝胶过滤色谱、荧光光谱、差示扫描量热分析、傅里叶变换红外光谱(FTIR)和葡激酶的纤溶活性分析研究了聚乙烯醇(PVA)和葡激酶的相互作用及其对葡激酶高级结构的影响. 凝胶过滤色谱研究结果表明, PVA与葡激酶之间形成了复合物; 荧光光谱和差示扫描量热分析结果提示, 葡激酶与PVA之间的相互作用没有破坏葡激酶的高级结构; 进一步使用红外光谱法结合可增强分辨率的傅里叶去卷积技术和高斯曲线拟合技术, 用于对葡激酶与PVA复合物冻干粉中葡激酶酰胺Ⅰ带的定量分析发现, 复合物冻干粉葡激酶分子中易导致蛋白质变性的分子间β-折叠组分含量明显减少. 纤溶活性分析结果进一步确认, PVA与葡激酶的相互作用未影响葡激酶的活性, 并对蛋白质的活性起保护作用.     

Analysis of the structures,energetics, and vibrational frequencies for the hydrogen-bonded interaction of nucleic acid bases with Carmustine pharmaceutical agent: a detailed computational approach

In the present study, it is attempted to scrutinize the hydrogen bonding interaction between Carmustine drug and DNA pyrimidine bases by means of density functional theory calculations regarding their geometries, binding energies, vibrational frequencies, and topological features of the electron density in the gas phase and the water solution. Based on the density functional theory results, it is found that the process of intermolecular interaction between Carmustine drug and nucleobases is exothermic and all of the optimized configurations are stable. Furthermore, the negative stability energy represented by a polarizable continuum model shows the significant increase in the solubility of the nucleobase after hydrogen bonding intermolecular interaction in the presence of water solvent. It is also found that the intermolecular hydrogen bonds between drug and the nucleobases play the significant role in the stability of the physisorption configurations. Hydrogen bond energies for hydrogen-bonded complexes are obtained from Espinosa method and the atoms-in-molecules theory are also applied to get a more precise insight into the nature of the intermolecular hydrogen bond interactions.     

Amine‐Linked N‐Heterocyclic Carbenes: The Importance of an Pendant Free‐Amine Auxiliary in Assisting the Catalytic Reaction

We have successfully expanded the library of amino–NHCs with varying substituents on the amine group, leading to insight about the instability of NHCs arising from the intermolecular interaction of the dangling amine side‐arm. However, the pendant amine plays an important role with respect to the catalytic process, resuscitating the catalytic activity of unsaturated NHC’s through a synergistic effect invoked by the secondary amine. This proof of concept allows us to expand the spectrum of catalysis to C C, as well as C B bond formation.     

Confined crystallization of binary n-alkane mixtures: stabilization of a new rotator phase by enhanced surface freezing and weakened intermolecular interactions

The present work reports the confined crystallization behaviours of binary even-even normal alkane (n-alkane) mixtures of n-octadecane (n-C(18)H(38)) and n-eicosane (n-C(20)H(42)), which are microencapsulated in monodisperse microcapsules, using the combination of differential scanning calorimetry (DSC) and temperature-dependent X-ray diffraction (XRD). A new metastable rotator phase (RII) absent in the bulk state, has been detected for the n-alkane mixture in confined geometry under all the investigated compositions. Such a crossover is attributed to the lower interfacial energy due to the same in-planar hexagonal structure of the surface monolayer and RII, as well as the weakened intermolecular interaction in alkane mixtures. This is the first time that RII is found in such a binary even-even n-alkane mixture that neither of the components contains RII phase in the crystallization process. Furthermore, based on the variation of alkane molecule conformation and in-planar structure with temperature, the correlations between the phase transition temperature and composition have been discussed.     

An efficient catalytic protocol for the Pauson-Khand reaction

New experimental conditions have been developed for an efficient catalytic Pauson-Khand reaction. These are based on the use of a mixture of molecular sieves and tert-butanol as inducers of the process. This mixture, with the appearance of a paste, is able to adsorb CO, thus improving the conversion and making it possible to effect the reactions in the absence of a CO atmosphere. The protocol is applied to known and unknown substrates and compared to previously described conditions, showing good results with intra- and intermolecular examples.